Heterocyclic amide derivatives

ABSTRACT

Novel heterocyclic amide derivatives of the formula ##STR1## in which R 1  represents alkyl, or represents alkenyl which has more than 2 carbon atoms and is optionally substituted by halogen, or represents alkinyl which has more than 2 carbon atoms and is optionally substituted by halogen, or represents alkoxyalkyl or alkylthioalkyl; 
     R 2  represents optionally substituted naphthyl, or represents optionally substituted tetrahydronaphthyl, or represents optionally substituted indanyl; 
     A represents an alkylene bridge, or also an alkenylene bridge if X denotes a direct bond; 
     X represents oxygen, sulphur or a direct bond; 
     Y represents oxygen or sulphur; 
     B represents imidazol-1-yl, pyridin-3-yl, pyrazin-2-yl, pyrimidin-5-yl, 1,2,4-triazol-1-yl or 1-methyl-imidazol-5-yl-; 
     and their acid addition salts and metal salt complexes, are outstandingly active as fungicides.

The present invention relates to new heterocyclic amide derivatives, tofungicidal compositions containing them, and to their use as fungicides.

It has been disclosed that certain amide derivatives, such as, forexample,N-[2-(2,4,6-trichlorophenoxy)ethyl]-N-propyl-1H-imidazole-1-carboxamide(compare DE-OS (German Published Specification) No. 2,429,523) andN-trichloromethylmercapto-tetrahydrophthalimide (compare K. H. Buchel,Pflanzenschutz and Schadlingsbekampfung (Plant Protection and CombatingPests), page 140, Georg Thieme Verlag Stuttgart, 1977) have fungicidalproperties. However, the activity of these compounds is not alwayscompletely satisfactory, especially when relatively low amounts andconcentrations are applied.

The present invention now provides, as new compounds, the heterocyclicamide derivatives of the formula ##STR2## in which R¹ represents alkyl,or represents alkenyl which has more than 2 carbon atoms and isoptionally substituted by halogen, or represents alkinyl which has morethan 2 carbon atoms and is optionally substituted by halogen, orrepresents alkoxyalkyl or alkylthioalkyl;

R² represents optionally substituted naphthyl, or represents optionallysubstituted tetrahydronaphthyl, or represents optionally substitutedindanyl;

A represents an alkylene bridge, or also an alkenylene bridge if Xdenotes a direct bond;

X represents oxygen, sulphur or a direct bond;

Y represents oxygen or sulphur;

B represents imidazol-1-yl, pyridin-3-yl, pyrazin-2-yl, pyrimidin-5-yl,1,2,4-triazol-1-yl or 1-methyl-imidazol-5-yl;

and acid addition salts and metal salt complexes thereof.

The heterocyclic amide derivatives of the formula (I) ##STR3## in whichR¹, R², A, X, Y and B have the abovementioned meanings,

are obtained when

(a) amines of the general formula (II) ##STR4## in which R¹, R², A and Xhave the abovementioned meanings,

are reacted with carbonyl or thiocarbonyl compounds of the generalformula (IIIa) ##STR5## in which Y represents oxygen or sulphur and

B' represents imidazolyl-1-yl, pyridin-3-yl, pyrazin-2-yl,pyrimidin-5-yl or 1-methylimidazol-5-yl,

or with carbonyl or thiocarbonyl compound of the general formula (IIIb)##STR6## in which Y represents oxygen or sulphur,

in the presence of a suitable inert organic solvent; or

(b) amines of the general formula (II) ##STR7## in which R¹, R², A and Xhave the abovementioned meanings, are reacted with carbamyl chloridecompounds of the formula (IV) ##STR8## in which B" representspyridin-3-yl, pyrazin-3-yl, pyrazin-2-yl, pyrimidin-5-yl or1-methylimidazol-5-yl,

in the presence of a suitable inert organic solvent and in the presenceof an acid-binding agent; or

(c) carbamyl chloride or thiocarbamyl chloride derivatives of thegeneral formula (V) ##STR9## in which R¹, R², A, X and Y have theabovementioned meanings, are reacted with azoles of the general formula(VI) ##STR10## in which Z represents a nitrogen atom or the CH group and

M represents hydrogen or an alkali metal,

in the presence of a suitable inert organic solvent and, if appropriate,in the presence of an acid-binding agent; or

(d) carboxamide of the formula (Ia) ##STR11## in which R¹, R², A, X andB have the abovementioned meanings,

are reacted with phosphorus pentasulphide in the presence of an inertorganic solvent.

If appropriate, an acid or a metal salt can then be added onto thecompounds of the formula (I) thus obtained.

The new heterocyclic amide derivatives of the formula (I) and their acidaddition salts and metal salt complexes have powerful fungicidalproperties. Surprisingly, the compounds according to the inventionthereby exhibit a more powerful action thanN-[2-(2,4,6-trichlorophenoxy)-ethyl]-N-propyl-1H-imidazole-1-carboxamideand N-trichloromethylmercaptotetrahydrophthalimide, which are known fromthe prior art and are closely related compounds structurally and fromthe point of view of their action. The substances according to theinvention thus represent an enrichment of the art.

Formula (I) provides a general definition of the heterocyclic amidederivatives according to the invention. Preferably, in this formula,

R¹ represents alkyl with 1 to 12 carbon atoms, or represents alkenyl oralkinyl which has in each case 3 to 12 carbon atoms and is optionallymonosubstituted or polysubstituted by identical or differentsubstituents from the group comprising fluorine and chlorine, whereinthe multiple bond in each case must not be in the α-position relative tothe nitrogen atom, or represents alkoxyalkyl or alkylthioalkyl with ineach case 1 to 6 carbon atoms in the alkoxy or alkylthio part and 2 to 6carbon atoms in the alkyl part;

R² represents naphthyl, tetrahydronaphthyl or indanyl, optionallymonosubstituted, disubstituted or trisubstituted by identical ordifferent substituents, substituents which may be mentioned in each casebeing: alkyl with 1 to 4 carbon atoms, halogen and halogenoalkoxy with 1to 4 carbon atoms and 1 to 5 identical or different halogen atoms, suchas, in particular, fluorine and chlorine atoms;

A represents a straight-chain or branched alkylene bridge with 1 to 8carbon atoms if X denotes a direct bond; or represents a straight-chainor branched alkylene bridge with 2 to 8 carbon atoms if X denotes oxygenor sulphur, but wherein there must be at least 2 carbon atoms betweenthe nitrogen atom and the radical X; or represents a straight-chain orbranched alkylene bridge with 3 to 8 carbon atoms, wherein the doublebond must not be in the α-position relative to the nitrogen atom;

X represents oxygen, sulphur or a direct bond;

Y represents oxygen; and

B represents imidazol-1-yl, pyridin-3-yl, pyrazin-2-yl, pyrimidin-5-yl,1,2,4-triazol-1-yl or 1methylimidazol-5-yl.

Particularly preferred compounds of the formula (I) are those

in which

R¹ represents straight-chain or branched alkyl with 1 to 10 carbonatoms, or represents alkenyl or alkinyl which has in each case 3 to 10carbon atoms and is optionally monosubstituted, disubstituted ortrisubstituted by identical or different substituents from the groupcomprising fluorine or chlorine, wherein the multiple bond in each casemust not be in the α-position relative to the nitrogen atom, orrepresents alkoxyalkyl or alkylthioalkyl with in each case 1 to 4 carbonatoms in the alkoxy or alkylthio part and 2 to 4 carbon atoms in thealkyl part;

R² represents naphthyl, tetrahydronaphthyl or indanyl, optionallymonosubstituted or disubstituted by identical or different substituents,substituents which may be mentioned in each case being fluorine,chlorine bromine and trifluoromethoxy;

A represents a straight-chain or branched alkylene bridge with 1 to 6carbon atoms if X denotes a direct bond; or represents a straight-chainor branched alkylene bridge with 2 to 6 carbon atoms if X denotes oxygenor sulphur, but wherein there must be at least 2 carbon atoms betweenthe nitrogen atom and the radical X, or represents an alkylene bridgewith 3 to 5 carbon atoms, wherein the double bond must not be in theα-position relative to the nitrogen atom;

X represents oxygen, sulphur or a direct bond;

Y represents oxygen; and

B represents imidazol-1-yl, pyrazin-2-yl or pyridin-3-yl.

Especially preferred compounds of the formula (I) are those

in which

R¹ represents straight-chain or branched alkyl with 2 to 8 carbon atomsstraight chain or branched alkenyl or alkinyl with, in each case, 3 to 8carbon atoms, wherein the multiple bond in each case must not be in theα-position relative to the nitrogen atom or represents methoxyethyl,ethoxyethyl, n-propoxyethyl, methylthioethyl, ethylthioethyl orn-propylthioethyl;

R² represents naphthyl, tetrahydronaphthyl or indanyl, optionallymonosubstituted or disubstituted by identical or different substituents,substituents which may be mentioned being fluorine, chlorine andtrifluoromethoxy;

A represents a straight-chain or branched alkylene bridge with 1 to 4carbon atoms if X denotes a direct bond; or represents a straight-chainor branched alkylene bridge with 2 to 4 carbon atoms if X denotes oxygenor sulphur, but wherein there must be at least 2 carbon atoms betweenthe nitrogen atom and the radical X, or represents an alkenylene bridgewith 3 carbon atoms, wherein the double bond must not be in theα-position relative to the nitrogen atom;

X represents oxygen, sulphur or a direct bond;

Y represents oxygen; and

B represents imidazol-1-yl or pyridin-3-yl.

Addition products of acids and those heterocyclic amide derivatives ofthe formula (I) in which the substituents R¹, R², A, X, Y and B have themeanings which have already been mentioned as preferred for thesesubstituents are also preferred compounds according to the invention.

The acids which can be added on include, preferably, hydrogen halideacids, such as, for example, hydrochloric acid and hydrobromic acid, inparticular hydrochloric acid, and furthermore phoshoric acid, nitricacid, monofunctional and bifunctional carboxylic acids andhydroxycarboxylic acids, such as, for example, acetic acid, maleic acid,succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid,sorbic acid and lactic acid, and sulphonic acids, such as, for example,p-toluenesulphonic acid and 1,5-naphthalenedisulphonic acid.

Addition products of salts of metals of main group II to IV andsub-group I and II and IV to VIII and those substituted heterocyclicamide derivatives of the formula (I) in which the substituents R¹, R²,A, X, Y and B have the meanings which have already been mentioned aspreferred for these substituents are also preferred compounds accordingto the invention.

Salts of copper, zinc, manganese, magnesium, tin, iron and nickel areparticularly preferred here. Possible anions of these salts are thosewhich are derived from acids which lead to physiologically acceptableacid products. Particularly preferred acids of this type in thisconnection are the hydrogen halide acids, such as, for example,hydrochloric acid and hydrobromic acid, and furthermore phosphoric acid,nitric acid and sulphuric acid.

The following compounds of the general formula (I) may be mentionedspecifically, in addition to the compounds mentioned in the preparationexamples:

    __________________________________________________________________________     ##STR12##                                   (I)                              R.sup.1   R.sup.2      A         X Y B                                        __________________________________________________________________________    CH.sub.2 CH.sub.2 CH.sub.3                                                               ##STR13##   CHCHCH.sub.2                                                                            --                                                                              O                                                                                ##STR14##                               CH.sub.2 CH.sub.2 CH.sub.3                                                               ##STR15##   CH.sub.2 CH.sub.2 CH.sub.2                                                              --                                                                              O                                                                                ##STR16##                               CH.sub.2 CH.sub.2 CH.sub.3                                                               ##STR17##   CH.sub.2 CH.sub.2                                                                       O O                                                                                ##STR18##                               CH.sub.2CHCH.sub.2                                                                       ##STR19##   CH.sub.2 CH.sub.2                                                                       O O                                                                                ##STR20##                               CH.sub.2 CH.sub.2 CH.sub.3                                                               ##STR21##   CH.sub.2 CH.sub.2                                                                       O O                                                                                ##STR22##                               CH.sub.2 CH.sub.2 CH.sub.3                                                               ##STR23##   CH.sub.2 CH.sub.2                                                                       O O                                                                                ##STR24##                               CH.sub.2 CH.sub.2 CH.sub.3                                                               ##STR25##   CH.sub.2 CH.sub.2                                                                       O O                                                                                ##STR26##                               CH.sub.2 CH.sub.2 CH.sub.3                                                               ##STR27##   CH.sub.2 CH.sub.2                                                                       O O                                                                                ##STR28##                               CH.sub.2 CH.sub.2 CH.sub.3                                                               ##STR29##   CH.sub.2 CH.sub.2                                                                       O O                                                                                ##STR30##                               CH.sub.2CCH                                                                              ##STR31##   CH.sub.2  --                                                                              O                                                                                ##STR32##                               __________________________________________________________________________

If, for example, N-methyl-N-(2-naphthylmethyl)-amine andN,N'-carbonyldiimidazole ae used as starting substances, the course ofprocess (a) according to the invention can be represented by thefollowing equation: ##STR33##

If pyrazine-2-carbon-imidazolide is employed instead ofN,N'-carbonyldiimidazole, the equation of the reaction is as follows:##STR34##

If, for example, N-methyl-N-(2-naphthylmethyl)-amine andpyridin-3-ylcarbamyl chloride are used as starting substances, thecourse of process (b) according to the invention can be represented bythe following equation: ##STR35##

If, for example, [N-methyl-N-(2-naphthylmethyl)]carbamyl chloride andimidazole are used as starting substances, the course of process (c)according to the invention can be represented by the following equation:##STR36##

If, for example,N-methyl-N-(2-naphthylmethyl)-1H-imidazole-1-carboxamide and phosphoruspentasulphide or used as starting substances, the course of process (d)according to the invention can be represented by the following equation:##STR37##

Formula (II) provides a general definition of the amines to be used asstarting substances for carrying out process (a) and (b) according tothe invention. In this formula, R¹, R², A and X preferably have thosemeanings which have already been mentioned as preferred for thesesubstituents in connection with the description of the substances of theformula (I) according to the invention.

The amines of the formula (II) are known in some cases (compare, forexample, Helv. Chim. Acta 62, 1268 (1979) or Chem. Abstr. 80, 36 897p(1974)) and they can be obtained, for example, by reacting thecorresponding amide derivatives with lithium aluminium hydride in thepresence of tetrahydrofuran at reflux temperature. The amide derivativesare obtained by adding thionyl chloride to the corresponding carboxylicacid under reflux and adding the corresponding amine to the resultingcarbonyl acid chloride in the presence of tetrahydrofuran at roomtemperature (compare also the preparation examples).

Formulae (IIIa) and (IIIb) provide general definitions of the carbonyland thiocarbonyl compounds also to be used as starting substances forcarrying out process (a) according to the invention. In these formulae,B' and Y preferably have the abovementioned meanings.

The carbonyl and thionylcarbonyl compounds of the formulae (IIIa) and(IIIb) are known (compare, for example, Chem. Ber. 95, 1275 (1962) andLiebigs Annalen der Chemie 609, 75 (1957)). The compounds of the formula(IIIb) can be obtained by reacting triazole with phosgene orthiophosgene in the presence of tetrahydrofuran at room temperature; thecompounds of the formula (IIIa) can be obtained by reacting thecorresponding carboxylic acid with N,N'-carbonyldiimidazole in thepresence of tetrahydrofuran, with gentle warming. The carboxylic acidsrequired for this are generally known. Thus, 5-pyridinecarboxylic acidcan be obtained by first reacting 5-bromopyridine with n-butyllithium at-110° C. in the presence of, for example, absolute ether ortetrahydrofuran and then adding solid carbon dioxide (J. Org. Chem. 27,2264 (1962)). 1-Methyl-5-imidazolecarboxylic acid can be obtained byreacting 1-methyl-4,5-imidazoledicarboxylic acid with acetic anhydrideat elevated temperature (compare Bull. Chem. Soc. Japan 53, 557 (1980).1-Methyl-4,5-imidazoledicarboxylic acid can be obtained by reactingdiethyl 4,5-imidazoledicarboxylate with methyl iodide and sodiummethylate in the presence of ethanol at the reflux temperature and thenhydrolysing the product (compare Journal of Heterocyclic Chemistry 1,275 (1964)).

Formula (IV) provides a general definition of the carbamyl chloridecompounds also to be used as starting substances for carrying outprocess (b) according to the invention. In this formula, B" preferablyhas the abovementioned meaning.

The carbamoyl chloride compounds of the formula (IV) are known (compare,for example, Liebigs Annalen der Chemie 766, 73 (1972); Bull. Chem. Soc.Japan 53, 557 (1980); Rec. trav. chim. 80, 1372 (1961)), or the can beobtained by the processes described therein, by adding thionyl chlorideto the corresponding carboxylic acids under reflux (compare also thepreparation examples).

Formula (V) provides a general definition of the carbamyl chlorides tobe used as starting substances for carrying out process (c) according tothe invention. In this formula, R¹, R², A, X and Y preferably have themeanings which have already been given as preferred for thosesubstituents in connection with the description of the substances of theformula (I) according to the invention.

The carbamyl chlorides of the formula (V) can be obtained in generallyknown manner by reacting amines of the formula (III) with phosgene orthiophosgene in the presence of a suitable inert organic solvent, suchas, for example, acetonitrile, ethyl acetate, toluene, methylenechloride or dioxane, at temperatures between 20° C. and 140° C.

Formula (VI) provides a general definition of the azoles also to be usedas starting substances for carrying out process (c) according to theinvention. In this formula, Z represents a nitrogen atom or the CHgroup. M preferably represents hydrogen, sodium or potassium.

The azoles of the formula (VI) are generally known compounds of organicchemistry.

The heterocyclic amine derivatives of the formula (Ia) to be used asstarting substances for carrying out process (d) according to theinvention are compounds according to the invention and can be preparedby processes (a), (b) and (c) according to the invention.

Process (a) according to the invention is carried out in the presence ofan inert organic solvent. Inert organic solvents include, preferably,nitriles, such as acetonitrile; esters, such as ethyl acetate; ethers,such as dioxane; aromatic hydrocarbons, such as toluene; chlorinatedhydrocarbons, such as methylene chloride; acid amides, such asdimethylformamide; and sulphoxide, such as dimethylsulphoxide.Preferably, the solvent is employed in absolute form.

The reaction temperatures can be varied within a substantial range incarrying out process (a) accorrding to the invention. In general, thereaction is carried out at temperatures between 20° C. and 140° C.,preferably between 50° C. and 120° C.

The reaction in process (a) according to the invention can be carriedout under normal pressure, but also under increased pressure. Thereaction is in general carried out under pressures between 1 and 50 bar,preferably between 1 and 25 bar.

Process (b) according to the invention is carried out in the presence ofan inert organic solvent. Inert organic solvents include, preferably,nitriles, such as acetonitrile; esters, such as ethyl acetate; ethers,such as dioxane; aromatic hydrocarbons, such as toluene and chlorinatedhydrocarbons, such as methylene chloride.

Possible acid-binding agents for process (b) according to the inventionare all the bases which can usually be employed. These include,preferably, teriary amines, such as triethylamine or pyridine; alkalimetal hydroxides and alkali metal carbonates.

The reaction temperatures can be varied within a substantial range incarrying out process (b) according to the invention. The reaction is ingeneral carried out at temperatures between 0° C. and 120° C.,preferably at temperatures between 10° C. and 100° C.

Process (c) according to the invention is carried out in the presence ofan inert organic solvent. Inert organic solvents include, preferably,nitriles, such as acetonitrile; esters, such as ethyl acetate; ethers,such as dioxane; aromatic hydrocarbons, such as toluene, and chlorinatedhydrocarbons, such as methylene chloride.

Possible acid-binding agents for process (c) according to the inventionare all the bases which can usually be employed. These include,preferably, tertiary amines, such as triethylamine or pyridine, and anexcess of imidazole or triazole.

The reaction temperatures can be varied within a substantial range incarrying out process (c) according to the invention. The reaction is ingeneral carried out at temperatures between 20° C. and 150° C.,preferably at temperatures between 50° C. and 120° C.

The reaction in process (c) according to the invention can be carriedout under normal pressure, but also under increased pressure. Theraction is in general carried out under pressures between 1 and 50 bar,preferably between 1 and 25 bar.

Process (c) according to the invention is carried out in the presence ofan inert absolute organic solvent. Inert absolute organic solventsinclude, preferably, nitriles, such as acetonitrile; ethers, such asdioxane; aromatic hydrocarbons, such as toluene, and chlorinatedhydrocarbons, such as methylene chloride.

The reaction temperatures can be varied within a substantial range incarrying out process (d) according to the invention. The reaction is ingeneral carried out at temperatures between 0° C. and 80° C., preferablyat temperatures between 10° C. and 60° C.

Process (d) according to the invention is preferably carried out in anultrasonic bath so that the dispersion of the phosphorus pentasulphidein the solvent is facilitated.

Those acids which have already been mentioned as preferred acids inconnection with the description of the acid addition salts according tothe invention are preferably suitable for the preparation of acidaddition salts of the compounds of the general formula (I).

The acid addition salts of the compounds of the formula (I) can beobtained in a simple manner by customary salt formation methods, forexample by dissolving a compound of the general formula (I) in asuitable inert solvent and adding the acid, for example hydrochloricacid, and they can be isolated in a known manner, for example byfiltration, and if appropriate purified by washing with an inert organicsolvent.

Those salts of metals which have already been described above arepreferably suitable for the preparation of metal salt complexes of thecompounds of the general formula (I).

The metal salt complexes of compounds of the general formula (I) can beobtained in a simple manner by customary processes, thus, for example,by dissolving the metal salt in alcohol, for example ethanol, and addingthe solution to compounds of the general formula (I). Metal saltcomplexes can be purified in a known manner, for example by filtration,isolation and, if appropriate, by recrystallisation.

The active compounds according to the invention exhibit a powerfulmicrbiocidal action and can be employed in practice for combatingundesired microorganisms. The active compounds are suitable for use asplant protection agents.

Fungicidal agents in plant protection are employed for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Some causative organisms of fungal and bacterial diseases which comeunder the generic names listed above may be mentioned as examples, butnot by way of limitation: Xanthomonas species, such as, for example,Xanthomonas campestris pv. oryzae; Pseudomonas species, such as, forexample, Pseudomonas syringae pv. Lachrymans; Erwinia species, such as,for example, Erwinia amylovora; Pythium species, such as, for example,Pythium ultimum; Phytophthora species, such as, for example,Phytophthora infestans; Pseudoperonospora species, such as, for example,Pseudoperonospora humuli or Pseudoperonospora cubense; Plasmoparaspecies, such as, for example, Plasmopara viticola; Peronospora species,such as, for example, Peronospora pisi or P. brassica; Erysiphe species,such as, for example, Erysiphe graminis; Sphaerotheca species, such as,for example, Sphaerotheca fuliginea; Podosphaera species, such as, forexample, Podosphaera leucotricha; Venturia species, such as, forexample, Venturia inaequalis; Pyrenophora species, such as, for example,Pyrenophora teres or P. graminea; (conidia form: Drechslera, syn:Helminthosporium); Cochliobolus species, such as, for example,Cochliobolus sativus; (conidia form: Drechslera, syn: Helminthosporium);Uromyces species, such as, for example, Uromyces appendiculatus;Puccinia species, such as, for example, Puccinia recondita; Tilletiaspecies, such as, for example, Tilletia caries; Ustilago species, suchas, for example, Ustilago nuda or Ustilago avenae; Pellicularia species,such as, for example, Pellicularia sasakii; Pyricularia species, suchas, for example, Pyricularia oryzae; Fusarium species, such as, forexample, Fusarium culmorum; Botrytis species, such as, for example,Botrytis cinerea; Septoria species, such as, for example, Septorianodorum; Leptosphaeria species, such as, for example, Leptosphaerianodorum; Cercospora species, such as, for example, Cercospora canescens;Alternaria species, such as, for example, Alternaria brassicae andPseudocercosporella species, such as, for example, Pseudocercosporellaherpotrichoides.

The good toleration, by plants, of the active compounds, at theconcentrations required for combating plant diseases, permits treatmentof above-ground parts of plants, of vegetative propagation stock andseeds, and of the soil.

As plant protection agents, the active compounds according to theinvention can be used with particularly good success for combatingVenturia species, such as Venturia inaequalis on apple, and Pucciniaspecies, such as Puccinia recondita on wheat, and also for combatingpowdery mildew, Botrytis cinerea, Cochliobolus sativus, Pyrenophorateres and Fusarium on cereals and Pyricularia on rice. The good in vitroaction against Pyricularia oryzae on rice is to be emphasised.

The active compounds can be converted to the customary formulations,such as solutions, emulsions, suspensions, powders, foams, pastes,granules, aerosols, natural and synthetic materials impregnated withactive compound, very fine capsules in polymeric substances and incoating compositions for seed, and formulations used with burningequipment, such as fumigating cartridges, fumigating cans, fumigatingcoils and the like, as well as ULV cold mist and warm mist formulations.

These formulations are produced in known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents, and/or foam-forming agents. In the case of the use of water asan extender, organic solvents can, for example, also be used asauxiliary solvents. As liquid solvents, there are suitable in the main:aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinatedaromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylene or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethylsulphoxide, as well as water; by liquefied gaseous extenders orcarriers are meant liquids which are gaseous at normal temperature andunder normal pressure, for example aerosol propellants, such ashalogenated hydrocarbons as well as butane, propane, nitrogen and carbondioxide; as solid carriers there are suitable: for example groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly-disperse silicic acid, alumina and silicates;as solid carriers for granules there are suitable: for example crushedand fractionated natural rocks such as calcite, marble, pumice,sepiolite and dolomite, as well as synthetic granules of inorganic andorganic meals, and granules of organic material such as sawdust, coconutshells, maize cobs and tobacco stalks; as emulsifying and/orfoam-forming agents there are suitable: for example non-ionic andanionic emulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysation products; as dispersing agents there are suitable:for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 percent by weightof the active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be present in theformulations or in the various use forms as a mixture with other knownactive compounds, such as fungicides, bactericides, insecticides,acaricides, nematicides, herbicides, bird repellants, growth factors,plant nutrients and agents for improving soil structure.

The active compounds can be used as such or in the form of theirformulations or the use forms prepared therefrom by further dilution,such as ready-to-use solutions, emulsions, suspensions, powders, pastesand granules. They are used in the customary manner, for example bywatering, immersion, spraying, atomising, misting, vaporising,injecting, forming a slurry, brushing on, dusting, scattering, drydressing, moist dressing, wet dressing, slurry dressing or encrusting.

In the treatment of parts of plants, the active compound concentrationsin the use forms can be varied within a substantial range. They are, ingeneral, between 1 and 0.0001% by weight, preferably between 0.5 and0.001%.

In the treatment of seed, amounts of active compound of 0.001 to 50 gper kilogram of seed, preferably 0.01 to 10 g, are generally required.

For the treatment of soil, active compound concentrations of 0.00001 to0.1% by weight, preferably 0.0001 to 0.02% by weight, are required atthe place of action.

The present invention also provides a fungicidal composition containingas active ingredient a compound of the formula (I) according to thepresent invention in admixture with a solid diluent or carriercontaining a surface-active agent.

The present invention also provides a method of combating fungi whichcomprises applying to the fungi, or to a habitat thereof, a compound ofthe formula (I) according to the present invention alone or in the formof a composition containing as active ingredient a compound of theformula (I) according to the present invention in admixture with adiluent or carrier.

The preparation and use of the substances according to the invention canbe seen from the examples which follow.

PREPARATION EXAMPLES EXAMPLE 1 ##STR38##

(Process a)

A solution of 20 g (0.12 mole) of N-methyl-N-(2-naphthylmethyl)-amineand 21.1 g (0.13 mole) of N,N'-carbonyldiimidazole in 150 ml of absoluteacetonitrile is heated under reflux for 4 hours. After removal of thesolvent, the residue is taken up in ethyl acetate and the mixture iswashed three times with water, dried and concentrated.

30.9 g (that is to say 97% of theory) of[N-methyl-N-(2-naphthylmethyl)]-1H-imidazole-1-carboxamide of meltingpoint 94.5°-95.5° C. are obtained.

Preparation of the starting substances ##STR39##

A solution of 105.2 g (0.57 mole) of [N-methyl]naphthalene-2-carboxamidein 450 ml of absolute tetrahydrofuran is added dropwise to a suspensionof 26.5 g (0.7 mole) of lithium aluminium hydride in 450 ml of absoluteether and the mixture is then heated under reflux for 3 hours.

After working up, 96 g (98% of theory) ofN-methyl-N-(2-naphthyl)-methylamine are obtained as a light brown oil of98% purity. ##STR40##

A solution of 100 g (0.58 mole) of naphthalene-2-carboxylic acid in 220ml of thionyl chloride is heated under reflux for 1 hour and the excessthionyl chloride is then distilled off. The residue is suspended in 750ml of tetrahydrofuran and 91 g (0.9 mole) of 30% strength aqueousmethylamine solution are added, while cooling and stirring. 200 ml oftriethylamine are then rapidly added dropwise. The mixture is stirredovernight at room temperature. After removal of the solvent, the residueis partitioned between methylene chloride and water.

105.2 g (98% of theory) of [N-methyl]-naphthalene-2-carboxamide ofmelting point 108°-109° C. are obtained.

EXAMPLE 2 ##STR41##

(Process b)

A solution of 31 g (0.25 mole) of 3-pyridinecarboxylic acid in 120 ml ofthionyl chloride is heated under reflux for 1 hour and the excessthionyl chloride is then distilled off in vacuo. The residue issuspended in 400 ml of absolute tetrahydrofuran, and 30 g (0.18 mole) ofN-methyl-N-(2-naphthyl)-methylamine are added dropwise at roomtemperature, with stirring, 64.3 g (0.625 mole) of triethylamine arethen added dropwise and the reaction mixture is stirred at roomtemperature overnight. The tetrahydrofuran is removed, the residue ispartitioned between methylene chloride and water and the methylenechloride phase is separated off, washed once with a saturated sodiumbicarbonate solution and then twice with water, dried and concentrated.

42.7 g (86% of theory) of[N-methyl-N-(2-naphthyl)methyl]-3-pyridinecarboxamide are obtained as aviscous oil. NMR δ (CDCl₃) 8.9-8.5 and 7.9-7.0 (11H); 4.87 and 4.65 (2H,2s, broad); 3.07 and 2.90 (3H, 2s, broad).

The following compounds of the general formula (I) ##STR42## areobtained in an analogous manner and by the processes according to theinvention:

      Serial       Melting point (°C.) No. R.sup.1 R.sup.2 A X Y B or     spectroscopic data                3 CH.sub.2 CH.sub.2      CH.sub.3     ##STR43##      CH.sub.2      CH.sub.2 O O     ##STR44##      54-56      4 CH.sub.3     ##STR45##      CH.sub.2      CH.sub.2 O O     ##STR46##      96,5   5 CH.sub.2      CH.sub.3     ##STR47##      CH.sub.2      CH.sub.2 O O     ##STR48##      87-88   6 CH.sub.2      CHCH.sub.2     ##STR49##      CH.sub.2      CH.sub.2 O O     ##STR50##      80   7 CH.sub.2 CH.sub.2 CH.sub.2      CH.sub.3     ##STR51##      CH.sub.2      CH.sub.2 O O     ##STR52##      ##STR53##        8 CH.sub.2 CH.sub.2      CH.sub.3     ##STR54##      CH.sub.2 -- O      ##STR55##      ##STR56##        9 CH.sub. 2 CH.sub.2      CH.sub.3     ##STR57##      CH.sub.2      CH.sub.2 O O     ##STR58##      ##STR59##       10 CH.sub.2 CH.sub.2      CH.sub.3     ##STR60##      CH.sub.2      CH.sub.2 O O     ##STR61##       11 CH.sub.2 CH.sub.2      CH.sub.3     ##STR62##      CH.sub.2      CH.sub.2 O O     ##STR63##      63,5  12 CH.sub.2 CH.sub.2      CH.sub.3     ##STR64##      CH.sub.2      CH.sub.2 O O     ##STR65##      oil  13 CH.sub.2      CH.sub.2 CH.sub.3     ##STR66##      CH.sub.2      CH.sub.2 -- O     ##STR67##      ##STR68##       14 CH.sub.2 CH.sub.2      CH.sub.3     ##STR69##      CH.sub.2      CH.sub.2 -- O     ##STR70##      56-57  15 CH.sub.2 CH.sub.2      OCH.sub.3     ##STR71##      CH.sub.2      CH.sub.2 O O     ##STR72##       16 CH.sub.2 CH.sub.2      CH.sub.3     ##STR73##      CH.sub.2      CH.sub.2 S O     ##STR74##       17 CH.sub.2 CH.sub.2      CH.sub.3     ##STR75##      CH.sub.2      CH.sub.2 O O     ##STR76##       18 CH.sub.2      CH.sub.3     ##STR77##      CH.sub.2 -- O      ##STR78##      ##STR79##       19 CH.sub.2 CH.sub.2 CH.sub.2      CH.sub.3     ##STR80##      CH.sub.2 -- O      ##STR81##      ##STR82##       20 CH.sub.2      CHCH.sub.2     ##STR83##      CH.sub.2 -- O      ##STR84##      ##STR85##       21 CH.sub.2      CH.sub.3     ##STR86##      CH.sub.2 -- O      ##STR87##      ##STR88##       22 CH.sub. 2 CH.sub.2      CH.sub.3     ##STR89##      CH.sub.2 -- O      ##STR90##      ##STR91##       23 CH.sub.2 CH.sub.2 CH.sub.2      CH.sub.3     ##STR92##      CH.sub.2 -- O      ##STR93##      ##STR94##       24 CH.sub.2      CHCH.sub.2     ##STR95##      CH.sub.2 -- O      ##STR96##      ##STR97##       25 CH.sub.2 CH.sub.2 CH.sub.3  CH.sub.2      CH.sub.2 O O     ##STR98##      ##STR99##       26 CH.sub.3  CH.sub.2      CH.sub.2 O O     ##STR100##      ##STR101##       27 CH.sub.2 CH.sub.3  CH.sub.2      CH.sub.2 O O     ##STR102##      ##STR103##      28 CH.sub.2CHCH.sub.2     ##STR104##      CH.sub.2CH.sub.2 O O      ##STR105##      oil      29 CH.sub.3     ##STR106##      CH.sub.2CH.sub.2 O O      ##STR107##      81.5-82.5      30 CH.sub.3     ##STR108##      CH.sub.2CH.sub.2 O O      ##STR109##      oil      31 CH.sub.2CH.sub.3     ##STR110##      CH.sub.2CH.sub.2 O O      ##STR111##      92.5      32 CH.sub.2CH.sub.3     ##STR112##      CH.sub.2CH.sub.2 O O      ##STR113##      oil      33 (CH.sub.2).sub.3CH.sub.3     ##STR114##      CH.sub.2CH.sub.2 O O      ##STR115##      87.5      34 (CH.sub.2).sub.3CH.sub.3     ##STR116##      CH.sub.2CH.sub.2 O O      ##STR117##      oil      35 CH.sub.2CHCH.sub.2     ##STR118##      CH.sub.2CH.sub.2 O O      ##STR119##      80-81       36 (CH.sub.2).sub.3CH.sub.3     ##STR120##      CH.sub.2CH.sub.2 -- O      ##STR121##      ##STR122##      37 (CH.sub.2).sub.3CH.sub.3     ##STR123##      CH.sub.2CH.sub.2 -- O      ##STR124##      ##STR125##      38 (CH.sub.2).sub.2CH.sub.3     ##STR126##      CH.sub.2CH.sub.2 -- O      ##STR127##      ##STR128##      39 CH.sub.2CHCH.sub.2     ##STR129##      CH.sub.2CH.sub.2 O O      ##STR130##      ##STR131##      40 CH.sub.2CH.sub.3     ##STR132##      CH.sub.2CH.sub.2 -- O      ##STR133##      ##STR134##      41 (CH.sub.2).sub.3CH.sub.3     ##STR135##      CH.sub.2CH.sub.2 -- O      ##STR136##      ##STR137##      42 (CH.sub.2).sub.4CH.sub.3     ##STR138##      CH.sub.2CH.sub.2 O O      ##STR139##      43 (CH.sub.2).sub.5CH.sub.3     ##STR140##      CH.sub.2CH.sub.2 O O      ##STR141##      44 (CH.sub.2).sub.6CH.sub.3     ##STR142##      CH.sub.2CH.sub.2 O O      ##STR143##      45 (CH.sub.2).sub.4CH.sub.3     ##STR144##      CH.sub.2 -- O      ##STR145##      46 (CH.sub.2).sub.5CH.sub.3     ##STR146##      CH.sub.2 -- O      ##STR147##      47 (CH.sub.2).sub.6CH.sub.3     ##STR148##      CH.sub.2 -- O      ##STR149##      48 (CH.sub.2).sub.2CH.sub.3     ##STR150##      CH.sub.2CH.sub.2 O O      ##STR151##      112-114

Use Examples

The substances shown below are employed as comparison compounds in theuse examples which follow: ##STR152##

Example A

Puccinia test (wheat)/protective/

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are inoculated with aspore suspension of Puccinia recondita with a 0.1% strength aqueous agarsolution. After the spore suspension has dried on, the plants aresprayed with the preparation of active compound until dew-moist. Theplants remain in an incubation cabin at 20° C. and 100% relativeatmospheric humidity for 24 hours.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80% in order to promote thedevelopment of rust pustules.

Evaluation is carried out 10 days after the inoculation.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compound according to the preparation example3.

Example B

Venturia test (apple)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated with an aqueous conidiasuspension of the apple scab causative organism (Venturia inaequalis)and then remain in an incubation cabin at 20° C. and 100% relativeatmospheric humidity for 1 day.

The plants are then placed in a greenhouse at 20° C. and a relativeatmospheric humidity of about 70%.

Evaluation is carried out 12 days after the inoculation.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compound according to the preparation example3.

It will be understood that the specification and examples areillustrative, but not limitative of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

What is claimed is:
 1. A heterocyclic amide derivative of the formula##STR153## in which R¹ is alkyl with 1 to 12 carbon atoms, alkenyl with3 to 12 carbon atoms, halogeno-substituted alkenyl with 3 to 12 carbonatoms, alkinyl with 3 to 12 carbon atoms, halogeno-substituted alkinylwith 3 to 12 carbon atoms, alkoxyalkyl with 1 to 6 carbon atoms in thealkoxy part and 2 to 6 carbon atoms in the alkyl part or alkylthioalkylwith 1 to 6 carbon atoms in the alkyl part;R² is naphthyl, naphthylsubstituted by a substituent selected from the group consisting of alkylwith 1 to 4 carbon atoms, halogen and halogenoalkoxy with 1 to 4 carbonatoms and 1 to 5 identical or different halogen atoms,tetrahydronaphthyl, tetrahydrononaphthyl substituted by a substituentselected from the group consisting of alkyl with 1 to 4 carbon atoms,halogen and halogenoalkoxy with 1 to 4 carbon atoms and 1 to 5 identicalor different halogen atoms, indanyl or indanyl substituted by asubstituent selected from the group consisting of alkyl with 1 to 4carbon atoms, halogen and halogenoalkoxy with 1 to 4 carbon atoms and 1to 5 identical or different halogen atoms; A is an alkylene bridge with1 to 8 carbon atoms or, if X denotes a direct bond, is also analkenylene bridge with 1 to 8 carbon atoms; X is oxygen, sulphur or adirect bond; and Y is oxygen or sulphur;or an acid addition salt or ametal salt complex thereof.
 2. Compound as claimed in claim 1, inwhichR¹ is alkyl with 1 to 12 carbon atoms; alkenyl or alkinyl with,ineach case, 3 to 12 carbon atoms, wherein the multiple bond in eachcase must not be in the α-position relative to the nitrogen atom;substituted alkenyl or substituted alkinyl with in each case 3 to 12carbon atoms, wherein the multiple bond in each case must not be in theα-position relative to the nitrogen atom, the substituents beingselected from the group consisting of fluorine and chlorine; or isalkoxyalkyl or alkylthioalkyl with in each case 1 to 6 carbon atoms inthe alkoxy or alkylthio part and 2 to 6 carbon atoms in the alkyl part;R² is naphthyl, substituted naphthyl the substituents being selectedfrom the group consisting of alkyl with 1 to 4 carbon atoms, halogen andhalogenoalkoxy with 1 to 4 carbon atoms and 1 to 5 identical ordifferent halogen atoms, or is tetrahydronaphthyl, substitutedtetrahydronaphthyl the substituents being selected from the groupconsisting of alkyl with 1 to 4 carbon atoms, halogen and halogenoalkoxywith 1 to 4 carbon atoms and 1 to 5 identical or different halogenatoms, or is indanyl or substituted indanyl the substituents beingselected from the group consisting of alkyl with 1 to 4 carbon atoms,halogen and halogenoalkoxy with 1 to 4 carbon atoms and 1 to 5 identicalor different halogen atoms; A is a straight-chain or branched alkylenebridge with 1 to 8 carbon atoms if X denotes a direct bond; or is astraight-chain or branched alkylene bridge with 2 to 8 carbon atoms if Xdenotes oxygen or sulphur, but wherein there must be at least 2 carbonatoms between the nitrogen atom and the radical X; or is astraight-chain or branched alkylene bridge with 3 to 8 carbon atoms,wherein the double bond must not be in the α-position relative to thenitrogen atom; X is oxygen, sulphur or a direct bond; and Y is oxygen;oran acid addition salt or a metal salt complex thereof.
 3. A compound asclaimed in claim 1, in whichR¹ is alkyl with 1 to 10 carbon atoms;alkenyl or alkinyl with, in each case, 3 to 10 carbon atoms, wherein themultiple bond in each case must not be in the α-position relative to thenitrogen atom; mono-, di- or tri-substituted alkenyl or mono-, di- ortri-substituted alkinyl with in each case 3 to 10 carbon atoms, whereinthe multiple bond in each case must not be in the α-position relative tothe nitrogen atom, the substituents being identical or different andbeing selected from the group consisting of fluorine and chlorine; or isalkoxyalkyl or alkylthioalkyl with in each case 1 to 4 carbon atoms inthe alkoxy or alkylthio part and 2 to 4 carbon atoms in the alkyl part;R² is naphthyl or mono-, di- or tri-substituted naphthyl thesubstituents being identical or different and being selected from thegroup consisting of fluorine, chlorine, bromine and trifluoromethoxy; oris tetrahydronaphthyl or mono-, di- or tri-substitutedtetrahydronaphthyl the substituents being identical or different andbeing selected from the group consisting of fluorine, chlorine, bromineand trifluoromethoxy; or is indanyl or mono-, di- or tri-substitutedindanyl the substituents being identical or different and being selectedfrom the group consisting of fluorine, chlorine, bromine andtrifluoromethoxy; A is a straight-chain or branched alkylene bridge with1 to 6 carbon atoms if X denotes a direct bond; or is a straight-chainor branched alkylene bridge with 2 to 6 carbon atoms if X denotes oxygenor sulphur, but wherein there must be at least 2 carbon atoms betweenthe nitrogen atom and the radical X, or is an alkylene bridge with 3 to5 carbon atoms, wherein the double bond must be in the α-positionrelative to the nitrogen atom; X, is oxygen, sulphur or a direct bond;and Y is oxygen; B is imidazol-1-yl, pyrazin-2-yl or pyridin-3-yl.
 4. Acompound as claimed in claim 1 in whichR¹ is straight-chain or branchedalkyl with 2 to 8 carbon atoms, straight-chain or branched alkenyl oralkinyl with, in each case, 3 to 8 carbon atoms, wherein the multiplebond in each case must not be in the α-position relative to the nitrogenatom or is methoxyethyl, ethoxyethyl, n-propoxyethyl, methylthioethyl,ethylthioethyl or n-propylthioethyl; R² is naphthyl or mono- ordi-substituted naphthyl the substituents being identical or differentand being selected from the group consisting of fluorine, chlorine andtrifluoromethoxy; or is tetrahydronaphthyl or mono- or di-substitutedtetrahydronaphthyl the substituents being identical or different andbeing selected from the group consisting of fluorine, chlorine andtrifluoromethoxy; or is indanyl or mono- or di-substituted indanyl thesubstituents being identical or different and being selected from thegroup consisting of fluorine, chlorine and trifluoromethoxy; A isstraight-chain or branched alkylene bridge with 1 to 4 carbon atoms if Xdenotes a direct bond; or is a straight-chain or branched alkylenebridge with 2 to 4 carbon atoms if X denotes oxygen or sulphur, butwherein there must be at least 2 carbon atoms between the nitrogen atomand the radical X, or is an alkenylene bridge with 3 carbon atoms,wherein the double bond must not be in the α-position relative to thenitrogen atom; X is oxygen, sulphur or a direct bond; and Y is oxygen;oran acid addition salt or a metal salt complex thereof.
 5. A compound asclaimed in claim 1, wherein such compound is[N-methyl-N-(2-naphthylmethyl)]-1H-imidazole-1-carboxamide of theformula ##STR154##
 6. A compound as claimed in claim 1, wherein suchcompound is[N-(n-propyl)-N-(2-naphthyloxy-2-ethyl)]-1H-imidazole-1-carboxamide ofthe formula ##STR155##
 7. A compound as claimed in claim 1, wherein suchcompound is[N-methyl-N-(2-naphthyloxy-2-ethyl)]-1H-imidazole-1-carboxamide of theformula ##STR156##
 8. A compound as claimed in claim 1, wherein suchcompound is[N-ethyl-N-(2-naphthyloxy-2-ethyl)]-1H-imidazole-1-carboxamide of theformula ##STR157##
 9. A fungicidal composition comprising a fungicidallyeffective amount of a compound or addition product according to claim 1in admixture with a diluent.
 10. A method of combating fungi whichcomprises administering to such fungi or to a fungus habitat afungicidally effective amount of a compound or addition productaccording to claim
 1. 11. The method according to claim 10, wherein suchcompound is[N-methyl-N-(2-naphthylmethyl)]-1H-imidazole-1-carboxamide,[N-(n-propyl)-N-(2-naphthyloxy-2-ethyl)]-1H-imidazole-1-carboxamide,[N-methyl-N-(2-naphthyloxy-2-ethyl)]-1H-imidazole-1-carboxamide or[N-ethyl-N-(2-naphthyloxy-2-ethyl)]-1H-imidazole-1-carboxamide,or anacid addition salt or a metal salt complex thereof.
 12. A heterocyclicamide derivative according to claim 1, whereinR¹ is alkyl with 1 to 12carbon atoms, alkenyl with 3 to 12 carbon atoms, wherein the multiplebond must not be in the α-position relative to the nitrogen atom; or isalkoxyalkyl with 1 to 6 carbon atoms in the alkoxy part and 2 to 6carbon atoms in the alkyl part; R² is naphthyl or halogen substitutednaphthyl; A is a straight-chain or branched alkylene bridge with 1 to 8carbon atoms if X denotes a direct bond; or is a straight-chain orbranched alkylene bridge with 2 to 8 carbon atoms if X denotes oxygen orsulphur, but wherein there must be at least 2 carbon atoms between thenitrogen atom and the radical X; X is oxygen, sulphur or a direct bond;and Y is oxygen.